Production of nitrogenous vat dyestuffs



Patented July 24, 1934 1,967,363

"raonUoTiofN OF NITROGENOUS VAT. J YE S i Max Mannheim, and Kan Koeberle Ludwigshafen: on the E, RhinefGerman'y', ,asv signors to, General 'Aniline Works," Inc.," New 7 "YorkN.acprporationcf Delaware I Q i .No Drawing; .Applicationbctolier 22, .1928,1Serial I No. 314,310. In Germany, November 3,1927

" {,ffiironing-(01. 260-61) The'present invention relates to the production sufficient. Accordingto the selection of the actof nitrogenous vat dyestufis containing a 'dibening-components, vat dyestufis of very varied charz'anthrone or-iso-dibenzanthrone meme A actor are obtained which give extremely fast dye- We have found that valuable vat dyestuffs are ings; in a great variety oil shade on vegetable 5 obtained by condensing dibenzanthrone orisofibres, from the vat. T

dibenzanthrone, or -a derivative'thereoflwhich The -following exampleswillj further illustrate compounds are hereinafter referred to for' the the'nature or'the said invention which however sake of brevity' as dibenz anthrones, containing at is not limited thereto. The parts are by weight. least one nitrogen atom to which-a reactivehyr I "E db 1 drogen atoin'i's attached, '-for"i nstance, amino- 7 i dibenzanthrone or]-amino iso dibenzanthrone or 47 parts of aminodibenzanthrone obtainable by the corresponding-monoalkyl-amino or' monoreducing the nitrodibenzanthrone obtained acacyl-arnino derivatives, with mono cycl-iccomcording to U. S. Patent No. 796,393, 25 parts of pounds substituted on the nucleus by atleast one chloranile, "20' parts of sodium acetate, and 0.5

oxygenatom or one hydroxygroup and atleast' part of 'cupric oxid, are stirred and boiled with 9. one exchangeable negative substituent, "such a's 500 partsofnltrobenzene until no more unaltered halogen atoms," nitro grou'ps and the like." "As aminodibenzanthrone can be detected, which will negatively substituted compounds of the afore be the'case inabout 8 hours. After filtrationby said kind picryl chloride, chloranile, chlorophesuction while hot, the residue is extracted by boiln01, the fimides of aliphatic dicarboxylic' acids ing with water and dilute. acid, and dried. The containing more than 2' carbon atoms, 'f'or'in new dyestufi is a blue black powder which disstancethe imides ofmalonic, r'naleidsuccinic acid solves to a violet solutionin concentrated sulfuric a'ndthelike containing one or-more negative subacid and gives fast blue ldyeings with a greenish stituents, such as halogen atoms may be men-- tinge on cotton froma blue vat.

The condensation is "sui tabl'y carried out in e t 2 solvents or diluting media of a high boiling point, A suspension of 50' parts of aminodiben such as for instance nitrob'enzene; naphthalene, zanthrone, prepar'edby reducing the nitrodibenanthracene and the like, preferably in the pres- Z'anthrone obtainable'according to U. S. Patent ence of acid-fixing agentasuch as sodium acetate N0. 1,513 ;851;l2.5'parts of, chloranile, 50 parts of and condensing catalysts-, for"=instance metal or Sodium acetate and 1 pa f 6 1 1 C a metal compoundasuch'as copper, copper oxid; in 1009 parts of nitrobenzene, is stirredat from copper carbonate, mercury cxid, aluminium and 21'0" to2l5" Centigrade, until the formation of the the like. dyestufl? is complete. The further treatment is 35. In the case of poly-negatively substituted comthesame'as in Examplel. The dy'estufi, which is pounds, the wholeor only a portion'of" the negaobtained in the form of a blue black powder, distive substituents may be repljaced, asdesired; by solvesto a violet solution in concentrated sulfuric the nitrogenous dibenzanthronyl or 'isodibe'm acid, and gives very fast bluedyeings on cotton zanthronyl radicle. The reactive negative groups from a blue hyd fosulfite, vat.

40 remaining; infthe condensationp'roductin the j 3 lattergcase can be replaced by ra'dicles of aromatic I w hydroxy compounds, suchas phenolsbrthiophej4 .5 partsoi jdibrommaleic imide are dissolved nols. For example, the nitrogenous dibenzanin 250 parts of nitrobenzene and boiled while stirs throne or isodibenzanthrone derivative forming ring forabout8 hours with 1 part ofcopper oxid,

I the initial material may be made to act upon the 5 parts of sodium carbonate and 9.5 parts of ami- 190 said negatively-substituted, mono-nuclear comnodibenzanthrone. After working up the reac pound, either alone or in admixture with the said tion mixture as described in Example 1, a black other reactive compounds, or subsequently to powder is obtained dissolving to a violet solution treatment with these. in concentrated sulfuric acid and dyeing cotton The new vat dyestufis obtainable according to from a blue vat blue green shades of very good 105 the present invention are, for the most part, profastness. duced with an excellent yield. For the purpose Example 4 of purification, they may be recrystallized from organic solvents of high boiling point; but in 10 parts of the reaction product obtained ac many instances, a simple boiling with solvents is cording to Example 1 are suspended in parts or m? tion. The dyestuff is a black powder dissolving to a violet solution in concentrated sulfuric acid, dyeing cotton from a blue vat blue grey shades.

Example 5 9.4 parts of amino-iso-dibenzanthrone are boiled for 15 hours while stirring1in'250parts of nitrobenzene with 10 parts of sodium-acetate,

2 parts of copper oxid and 2.5 parts of chloranile. V

'stuils which comprises condensing a mono-nu- The dyestuff recovered in the usual manner is a blue powder dissolving to a green solution in concentrated sulfuric acid and dyes cotton from a blue vat strong blue very fast shades.

What we claim is:-

1. A process of producing nitrogenous vat dye-e stuffs which comprises condensing chloranile with a dibenzanthrone containing at least one nitrogen atom to which a reactive hydrogen atom is attached.

2. A process of producing nitrogenous vatdyestufis which comprises condensing chloranile with aminodibenzanthrone.

3. Nitrogenous vat dyestuffs corresponding to the general formula in which X stands for hydrogen or an alkyl group;

- R for a dibenzanthrone'radicle .and R for a mononuclear radicle, the oxygen atom being directly attached to the nucleus of R.

4. Nitrogenous vat dyestuffs corresponding to the general formula in which R stands for dibenzanthrone radicles, forming a blue black powder, dissolving to a violet solution in concentrated .sulfuric acid and dyeing cotton blue shades from a blue vat. 1 5. A process of producing nitrogenousvat dyestuffs which comprises condensing a mono-nuclear compound substituted on .the nucleus by at least one oxygen atom and at least 1 substituent selected'from'the group consisting of the halogens and the nitro group with adibenzanthronecontaining at least 1 nitrogen atom to which a reactive hydrogen atom is attached. f

6. A process of producing'nitroge'nous vat dyestufis which comprisesvcondensing a mono-nuclear compound substituted on the nucleus by at least 1 oxygen atom and at least 1 substituent selected from the groupconsisting of the halogens and the nitro group with a dibenzanthrone containing at least 1 nitrogen atom to which a reactive hydrogen atom is attached, in the presence of a diluent of high boiling point.

. 7. A process of'producing nitrogenous vat dyestuffs which comprises condensing a mono-nuclear compound substituted on the nucleus by at least 1 oxygen atom and at least 1 substituent -selected from the group consisting of the halogens and-the nitro group with a dibenzanthrone containing at least 1 nitrogen atom to which a reactive hydrogen atom is attached, in the presence of adiluentcf highboiling point and an acid-fixing agent;

" 8. A processof producing nitrogenous vat dyeclear' compound-substituted on the nucleus by at least 1' oxygenatom and at least 1 substituent selectedfrom the group consisting of the halogens and the nitro group with a dibenzanthrone containing at least 1. nitrogenatom to which a reactive hydrogen atom is attached, in the. presence of a diluent of high boiling point, an acid-fixing agent and a condensing catalyst.

, 9, A manufacture of vat dyestufis of the dibenzanthrone series by, treating amino-dibenzanthrones with a halogenated quinone of the benzene series at temperatures over 100 C.

10. A manufacture of vat dyestuifs of the dibenzanthrone series by treatingamino-dibenzanthrone with a halogenated quinone of the benzene series attemperatures over 100 C.

11. A-manufacture of vat dyestufis of the dibenzanthrone series by treating amino-dibenza'nthrone with tetra chloroquinone at temperatures over 100 C. I I v 12. The products of the reaction between the halogenated quinones of the benzene series and aminmdibenzanthrones, which products form blackish powders which dissolve in concentrated sulfuric acid to dark .violetsolutions andin boiling nitrobenzene or aniline to blue-green solutions, dyeing vegetable fiber froma blue vat deep green to. blue greentims of excellent properties of fastness, particularly to chlorine.

13. The products of the reaction between the halogenatedquinones o thebenzene series and amino-dibenzanthrone, which; products form blackish powders which dissolve in concentrated sulfuric acid to dark violet solutions and in boiling nitrobenzene or aniline to blue-green solutions, dyeing vegetable fiber from ablue vat deep green to blue-green tints of excellent properties of fastness, particularly to chlorine.

14, The productsof the reaction between tetrachloroquinone and amino-dibenzanthrone, which products form blackish powders which dissolve in concentrated sulfuric acid toidark violet solutions and in boiling nitrobenzene or aniline to bluegreen solutions, dyeing vegetable fiber from a blue vatdeep green to blue-green tints of excellent properties of fastness, particularly to chlorine.

MAX ALBERT KUNZ.

KARL KOEBERLE. 

